ITTV20110125A1 - PROCESS FOR THE PREPARATION OF MANUFACTURED ARTICLES IN GRANULATE CONGLOMERATE OF STONE MATERIAL AND RESIN WITH THERAPEUTIC ORIGIN - Google Patents
PROCESS FOR THE PREPARATION OF MANUFACTURED ARTICLES IN GRANULATE CONGLOMERATE OF STONE MATERIAL AND RESIN WITH THERAPEUTIC ORIGIN Download PDFInfo
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- ITTV20110125A1 ITTV20110125A1 IT000125A ITTV20110125A ITTV20110125A1 IT TV20110125 A1 ITTV20110125 A1 IT TV20110125A1 IT 000125 A IT000125 A IT 000125A IT TV20110125 A ITTV20110125 A IT TV20110125A IT TV20110125 A1 ITTV20110125 A1 IT TV20110125A1
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- anhydride
- silane
- oil
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Links
- 238000000034 method Methods 0.000 title claims description 36
- 239000000463 material Substances 0.000 title claims description 20
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000008187 granular material Substances 0.000 title description 4
- 230000001225 therapeutic effect Effects 0.000 title 1
- 150000008064 anhydrides Chemical class 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 13
- 235000007586 terpenes Nutrition 0.000 claims description 12
- 150000001993 dienes Chemical class 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000004575 stone Substances 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 150000003505 terpenes Chemical class 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 150000005846 sugar alcohols Polymers 0.000 claims description 9
- 150000005671 trienes Chemical class 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 5
- GQVMHMFBVWSSPF-SOYUKNQTSA-N (4E,6E)-2,6-dimethylocta-2,4,6-triene Chemical group C\C=C(/C)\C=C\C=C(C)C GQVMHMFBVWSSPF-SOYUKNQTSA-N 0.000 claims description 5
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- GQVMHMFBVWSSPF-UHFFFAOYSA-N cis-alloocimene Natural products CC=C(C)C=CC=C(C)C GQVMHMFBVWSSPF-UHFFFAOYSA-N 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 239000000944 linseed oil Substances 0.000 claims description 5
- 235000021388 linseed oil Nutrition 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 235000019198 oils Nutrition 0.000 claims description 5
- -1 quaternary ammonium halides Chemical class 0.000 claims description 5
- IHPKGUQCSIINRJ-UHFFFAOYSA-N β-ocimene Natural products CC(C)=CCC=C(C)C=C IHPKGUQCSIINRJ-UHFFFAOYSA-N 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 150000003626 triacylglycerols Chemical class 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- ZQPNGHDNBNMPON-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CO[Si](OC)(OC)CCC(C)OCC1CO1 ZQPNGHDNBNMPON-UHFFFAOYSA-N 0.000 claims description 3
- YBNXSKCLVOXLPW-UHFFFAOYSA-N 3,4-dimethyl-6-(2-methylprop-1-enyl)cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound CC1C(C(O)=O)C(C(O)=O)C(C=C(C)C)C=C1C YBNXSKCLVOXLPW-UHFFFAOYSA-N 0.000 claims description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 2
- 150000008045 alkali metal halides Chemical group 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000004984 aromatic diamines Chemical class 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 235000005687 corn oil Nutrition 0.000 claims description 2
- 239000002285 corn oil Substances 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 235000021323 fish oil Nutrition 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000002600 sunflower oil Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 claims 1
- KPNCYSTUWLXFOE-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCC(C)OCC1CO1 KPNCYSTUWLXFOE-UHFFFAOYSA-N 0.000 claims 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WGCKYCGUJYPRCV-UHFFFAOYSA-N 4,5-dimethyl-7-(2-methylprop-1-enyl)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound CC(C)=CC1C=C(C)C(C)C2C(=O)OC(=O)C12 WGCKYCGUJYPRCV-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/14—Polyepoxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/18—Polyesters; Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
- C04B2111/1006—Absence of well-defined organic compounds
- C04B2111/1012—Organic solvents
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/54—Substitutes for natural stone, artistic materials or the like
Description
Descrizione Description
“Processo per la preparazione di manufatti in conglomerato di granulato di materiale lapideo e resina con anidridi di origine terpenica†⠀ œProcess for the preparation of artifacts in conglomerate of stone material and resin with terpenic anhydridesâ €
La presente invenzione riguarda la fabbricazione di manufatti in conglomerato e, più particolarmente, un procedimento per la fabbricazione di manufatti in lastre e blocchi a partire da un impasto consistente in particelle di materiale lapideo o litoide e una resina induribile, in cui detta resina à ̈ ottenuta per reazione tra almeno un trigliceride di acidi grassi polinsaturi epossidati ed almeno un’anidride di origine terpenica. The present invention relates to the manufacture of manufactured articles in conglomerate and, more particularly, to a process for the manufacture of manufactured articles in slabs and blocks starting from a mixture consisting of particles of stone or lithoid material and a hardenable resin, in which said resin is obtained by reaction between at least one triglyceride of epoxidized polyunsaturated fatty acids and at least one anhydride of terpenic origin.
Stato dell’arte State of the art
E’ noto da molti anni un procedimento per la fabbricazione di manufatti in blocchi e lastre del tipo anzidetto, noto anche con il nome generico di tecnologia Bretonstoneâ„¢, nel quale si prepara un impasto iniziale costituito da un granulato di materiale lapideo oppure di materiale litoide inorganico od organico, avente una granulometria selezionata, e da un legante a base di resina induribile. For many years, a process for the manufacture of manufactured articles in blocks and slabs of the aforementioned type, also known by the generic name of Bretonstoneâ „¢ technology, is known, in which an initial mixture is prepared consisting of a granulate of stone material or inorganic or organic lithoid material, having a selected particle size, and a hardenable resin-based binder.
Questo impasto viene depositato su di un supporto temporaneo oppure in uno stampo, avente le dimensioni del manufatto finale, e viene sottoposto ad una fase di compressione sotto vuoto, con applicazione concomitante di un moto vibratorio a frequenza prestabilita. Il manufatto grezzo risultante viene trasferito ad una fase di indurimento, al termine della quale il manufatto presenta le caratteristiche meccaniche desiderate. La lastra risultante, eventualmente ottenuta da un blocco mediante segagione, viene poi inviata alle lavorazioni di finitura (calibratura, levigatura, lucidatura e simili). This mixture is deposited on a temporary support or in a mold, having the dimensions of the final product, and is subjected to a vacuum compression phase, with concomitant application of a vibratory motion at a predetermined frequency. The resulting raw article is transferred to a hardening phase, at the end of which the article has the desired mechanical characteristics. The resulting slab, possibly obtained from a block by sawing, is then sent to the finishing processes (calibration, smoothing, polishing and the like).
Per maggiori informazioni e dettagli tecnici circa la tecnologia Bretonstoneâ„¢ si rinvia alle domande di brevetto EP786325 e WO2006/122892, entrambe qui incorporate per riferimento. For more information and technical details about Bretonstoneâ „¢ technology, please refer to patent applications EP786325 and WO2006 / 122892, both incorporated herein by reference.
La domanda di brevetto WO2007/138529, anch’essa qui incorporata per riferimento, descrive la realizzazione di manufatti secondo la tecnologia Bretonstoneâ„¢ che non solo mantengono le caratteristiche meccaniche ed estetiche ottenibili utilizzando le resine leganti precedentemente note ma resistono anche all’ingiallimento dovuto all’esposizione ai raggi UV. Tale scopo viene conseguito con un procedimento del tipo precedentemente indicato e che si caratterizza per l’utilizzo di una resina poliestere, priva di solvente reattivo (quale ad esempio lo stirene), ottenuta per reazione tra almeno un acido grasso polinsaturo epossidato, preferibilmente un trigliceride di acidi grassi polinsaturi epossidati, ed almeno un’anidride alifatica o aromatica. Patent application WO2007 / 138529, also incorporated herein by reference, describes the production of products according to the Bretonstoneâ „¢ technology which not only maintain the mechanical and aesthetic characteristics obtainable using the previously known binder resins but also resist the yellowing due to exposure to UV rays. This object is achieved with a process of the type previously indicated and which is characterized by the use of a polyester resin, free of reactive solvent (such as styrene, for example), obtained by reaction between at least one epoxidized polyunsaturated fatty acid, preferably a triglyceride of epoxidized polyunsaturated fatty acids, and at least one aliphatic or aromatic anhydride.
Descrizione dell’invenzione Description of the invention
Lo scopo della presente invenzione à ̈ quello di mettere a punto un processo per la preparazione di manufatti in conglomerato e, più particolarmente, un procedimento per la preparazione di manufatti in forma di lastre o blocchi secondo quanto descritto nella suddetta domanda di brevetto WO2007/138529, che si basi sull’impiego di materie prime da fonti rinnovabili. The purpose of the present invention is to develop a process for the preparation of manufactured articles in conglomerate and, more particularly, a process for the preparation of manufactured articles in the form of slabs or blocks as described in the aforementioned patent application WO2007 / 138529 , which is based on the use of raw materials from renewable sources.
Tale scopo à ̈ stato raggiunto utilizzando resine ottenute per reazione tra almeno un trigliceride di acidi grassi polinsaturi epossidati ed almeno un’anidride derivante da fonti rinnovabili. This purpose has been achieved by using resins obtained by reaction between at least one triglyceride of epoxidized polyunsaturated fatty acids and at least one anhydride deriving from renewable sources.
Tra le possibili anidridi derivanti da fonti rinnovabili, le anidridi di origine terpenica si sono rivelate le più adatte. Among the possible anhydrides deriving from renewable sources, anhydrides of terpenic origin have proved to be the most suitable.
L’oggetto della presente invenzione à ̈ pertanto rappresentato da un procedimento per la preparazione di manufatti in conglomerato, preferibilmente in forma di lastre o blocchi, per indurimento di un impasto costituito da particelle di materiale lapideo oppure di materiale litoide e da una resina induribile, caratterizzato dal fatto che detta resina à ̈ ottenuta per reazione tra almeno un trigliceride di acidi grassi polinsaturi epossidati ed almeno un’anidride di origine terpenica in presenza di un iniziatore di catalisi, di un polialcool e di un silano The object of the present invention is therefore represented by a process for the preparation of manufactured articles in conglomerate, preferably in the form of slabs or blocks, by hardening a mixture consisting of particles of stone material or lithoid material and a hardenable resin , characterized in that said resin is obtained by reaction between at least one triglyceride of epoxidized polyunsaturated fatty acids and at least one anhydride of terpenic origin in the presence of a catalysis initiator, a polyalcool and a silane
In questo modo si ottiene un conglomerato in forma di lastre o blocchi con caratteristiche paragonabili a quelli ottenuti con il processo descritto in WO2007/138529 sia dal punto di vista chimico sia da quello di vista fisico utilizzando anidridi da fonti rinnovabili. In this way a conglomerate in the form of slabs or blocks is obtained with characteristics comparable to those obtained with the process described in WO2007 / 138529 both from a chemical and a physical point of view using anhydrides from renewable sources.
Per gli scopi della presente invenzione, con il termine “anidridi di origine terpenica†si intendono le anidridi ottenibili per reazione di Diels-Alder tra un’anidride monoinsatura, ovvero avente un doppio legame carboniocarbonio, e un diene o triene terpenico coniugato. For the purposes of the present invention, the term â € œanhydrides of terpenic originâ € means the anhydrides obtainable by the Diels-Alder reaction between a monounsaturated anhydride, ie having a double carbon-carbon bond, and a conjugated terpene diene or triene.
Le anidridi monoinsature utilizzabili per gli scopi della presente invenzione sono, preferibilmente, anidridi C4-C8, ancora più preferibilmente C4oppure C5, quali anidride maleica e anidride itaconica, l’anidride maleica essendo particolarmente preferita. The monounsaturated anhydrides which can be used for the purposes of the present invention are preferably C4-C8 anhydrides, even more preferably C4 or C5, such as maleic anhydride and itaconic anhydride, maleic anhydride being particularly preferred.
Per gli scopi della presente invenzione, con il termine “diene o triene terpenico coniugato†si intende un diene o triene coniugato ottenibile per decomposizione termica di un terpene avente almeno un doppio legame oppure un terpene contenente almeno due doppi legami coniugati. In entrambi i casi, si tratta di dieni coniugati C5-C15, ancora più preferibilmente di dieni C10. For the purposes of the present invention, the term â € œconjugated terpene diene or trieneâ € means a conjugated diene or triene obtainable by thermal decomposition of a terpene having at least one double bond or a terpene containing at least two conjugated double bonds. In both cases, they are C5-C15 conjugated dienes, even more preferably C10 dienes.
La decomposizione termica dei terpeni à ̈ nota in letteratura ed à ̈ descritta, ad esempio, in US2325422, qui incorporato per riferimento; essa avviene a temperature generalmente comprese tra 160 e 400 °C, preferibilmente tra 180 e 280 °C, ancora più preferibilmente tra 225 e 250 °C. The thermal decomposition of terpenes is known in the literature and is described, for example, in US2325422, incorporated herein by reference; it occurs at temperatures generally comprised between 160 and 400 ° C, preferably between 180 and 280 ° C, even more preferably between 225 and 250 ° C.
Tra i dieni coniugati ottenibili per decomposizione termica di un terpene, à ̈ preferito l’allo-ocimene, ovvero il triene coniugato ottenibile per decomposizione termica dell’α-pinene oppure del β-pinene; tra i terpeni contenenti due doppi legami coniugati, sono preferiti a-terpinene e bmircene. Il diene coniugato terpenico più preferito per gli scopi della presente invenzione à ̈ allo-ocimene. Among the conjugated dienes obtainable by thermal decomposition of a terpene, the allo-ocimene is preferred, that is the conjugated triene obtainable by thermal decomposition of Î ± -pinene or β-pinene; among the terpenes containing two conjugated double bonds, a-terpinene and bmyrcene are preferred. The most preferred terpene conjugated diene for the purposes of the present invention is allo-ocimene.
Le reazioni di Diels-Alder sono ugualmente ben note in letteratura e sono descritte, ad esempio, in Jerry March, Advanced Organic Chemistry, Third Edition, John Wiley & Sons, 1985, pag. 745-758, qui incorporato per riferimento. In particolare, le reazioni di Diels-Alder tra un’anidride monoinsatura ed un diene coniugato ottenibile per decomposizione termica di un terpene sono descritte in US3078235 e US4332733, anch’essi qui incorporati per riferimento. Diels-Alder reactions are equally well known in the literature and are described, for example, in Jerry March, Advanced Organic Chemistry, Third Edition, John Wiley & Sons, 1985, p. 745-758, incorporated herein by reference. In particular, the Diels-Alder reactions between a monounsaturated anhydride and a conjugated diene obtainable by thermal decomposition of a terpene are described in US3078235 and US4332733, also incorporated herein by reference.
L’anidride di origine terpenica terpenica preferita per gli scopi della presente invenzione à ̈ l’anidride dell’acido 3,4-dimetil-6-(2-metil-1-propenil)-4-cicloesen-1,2-dicarbossilico, ovvero l’anidride che si ottiene per reazione di Diels-Alder tra allo-ocimene e anidride maleica. The preferred terpenic anhydride of terpenic origin for the purposes of the present invention is the anhydride of the acid 3,4-dimethyl-6- (2-methyl-1-propenyl) -4-cyclohexen-1,2 -dicarboxylic, ie the anhydride obtained by the Diels-Alder reaction between allo-ocimene and maleic anhydride.
Secondo un aspetto della presente invenzione, le anidridi di origine terpenica possono essere usate in miscela con una o più anidridi non di origine terpenica e, in particolare, con una o più delle anidridi descritte in WO2007/138529. According to an aspect of the present invention, the anhydrides of terpenic origin can be used in admixture with one or more anhydrides of non-terpenic origin and, in particular, with one or more of the anhydrides described in WO2007 / 138529.
Per gli scopi della presente invenzione, detto almeno un trigliceride di acidi grassi polinsaturi epossidati à ̈, preferibilmente, una miscela di trigliceridi di acidi grassi polinsaturi epossidati a catena lunga, ovvero aventi da 14 a 24 atomi di carbonio. Secondo un aspetto preferito dell’invenzione, detta miscela di trigliceridi à ̈ un olio di origine naturale, quale ad esempio: olio di lino, olio di soia, olio di colza, olio di mais, olio di girasole, olio di palma, sego, olio di pesce; l’olio di lino à ̈ l’olio naturale preferito. For the purposes of the present invention, said at least one triglyceride of epoxidized polyunsaturated fatty acids is preferably a mixture of triglycerides of long-chain epoxidized polyunsaturated fatty acids, ie having from 14 to 24 carbon atoms. According to a preferred aspect of the invention, said triglyceride mixture is an oil of natural origin, such as for example: linseed oil, soybean oil, rapeseed oil, corn oil, sunflower oil, palm oil, tallow , fish oil; linseed oil is the preferred natural oil.
Per l’impiego nella presente invenzione i trigliceridi, ovvero gli oli, vengono sottoposti ad una reazione di epossidazione dei doppi legami presenti (reazione di per sé ben nota), prima di essere utilizzati per la preparazione della resina. For use in the present invention, the triglycerides, that is the oils, are subjected to an epoxidation reaction of the double bonds present (a reaction which is well known per se), before being used for the preparation of the resin.
Come nel caso del processo descritto in WO2007/138529, anche nel processo secondo la presente invenzione à ̈ necessaria la presenza di un iniziatore di catalisi; il quale, a seconda della natura e della quantità , agisce riducendo sia i tempi di reazione sia le temperature di processo. As in the case of the process described in WO2007 / 138529, the presence of a catalysis initiator is also necessary in the process according to the present invention; which, depending on the nature and quantity, acts by reducing both reaction times and process temperatures.
Tra i possibili iniziatori si possono elencare i seguenti: alogenuri di metalli alcalini, composti organometallici d’alluminio, zinco e stagno, alogenuri d’ammonio quaternario, ammine alifatiche e aromatiche, complessi a base di boro e titanio. Per gli scopi della presente invenzione, le ammine aromatiche C3-C6e, in particolare, le diammine aromatiche C3-C6, si sono rivelate particolarmente adatte; tra queste, l’1-metil-imidazolo à ̈ particolarmente preferito. Among the possible initiators the following can be listed: alkali metal halides, organometallic compounds of aluminum, zinc and tin, quaternary ammonium halides, aliphatic and aromatic amines, complexes based on boron and titanium. For the purposes of the present invention, the aromatic amines C3-C6e, in particular, the aromatic diamines C3-C6, have proved to be particularly suitable; among these, 1-methyl-imidazole is particularly preferred.
Per un miglior risultato finale in termini di proprietà fisiche del conglomerato, la reticolazione della resina per reazione tra almeno un trigliceride di acidi grassi polinsaturi epossidati ed almeno un’anidride di origine terpenica, à ̈ effettuata in presenza di un polialcool e di un silano. Il polialcool à ̈ preferibilmente un polialcool C2-C20, ancora più preferibilmente C2-C6; secondo un aspetto preferito dell’invenzione, esso à ̈ selezionato tra glicerina, 1,3-butandiolo, 2,4-butandiolo, 1,4-butandiolo, glicole etilenico e glicole propilenico, ancora più preferibilmente glicerina. Secondo un altro aspetto dell’invenzione, il silano à ̈ un trialcossisilano avente un gruppo terminale epossidico, preferibilmente avente da 7 a 14 atomi di carbonio, ancora più preferibilmente da 9 a 12; detto silano à ̈ preferibilmente selezionato tra (3-glicidossipropil)-trimetossi silano, (3-glicidossi-propil)-trietossisilano, viniltrimetossi-silano, (3-glicidossimetil)-trimetossi silano, (3-glicidossietil)-trimetossi silano, (3-glicidossibutil)-trimetossi silano, (3-glicidossimetil)-trietossi silano, (3-glicidossietil)-trietossi silano, (3-glicidossibutil)-trietossi silano, essendo il (3-glicidossipropil)-trimetossi silano particolarmente preferito. For a better final result in terms of physical properties of the conglomerate, the crosslinking of the resin by reaction between at least one triglyceride of epoxidized polyunsaturated fatty acids and at least one anhydride of terpenic origin, is carried out in the presence of a polyalcohol and a silane. . The polyalcohol is preferably a C2-C20 polyalcohol, even more preferably C2-C6; according to a preferred aspect of the invention, it is selected from glycerin, 1,3-butandiol, 2,4-butandiol, 1,4-butandiol, ethylene glycol and propylene glycol, even more preferably glycerin. According to another aspect of the invention, the silane is a trialkoxysilane having an epoxy terminal group, preferably having from 7 to 14 carbon atoms, still more preferably from 9 to 12; said silane is preferably selected from (3-glycidoxypropyl) -trimethoxy silane, (3-glycidoxy-propyl) -trimethoxysilane, vinyltrimethoxy-silane, (3-glycidoxymethyl) -trimethoxy silane, (3-glycidoxyethyl) -trimethoxy silane, (3 -glycidoxybutyl) -trimethoxy silane, (3-glycidoxymethyl) -trioethoxy silane, (3-glycidoxyethyl) -triethoxy silane, (3-glycidoxybutyl) -trimethoxy silane, (3-glycidoxypropyl) -trimethoxy silane being particularly preferred.
Secondo un ulteriore aspetto dell’invenzione, le particelle di detto materiale lapideo oppure di materiale litoide hanno una granulometria media compresa tra 0.001 mm e 10 mm, preferibilmente tra 0.010 mm e 5 mm; più particolarmente dette particelle di materiale lapideo oppure di materiale litoide sono costituite da filler di quarzo (detto anche polvere ventilata) avente granulometria media compresa fra 0.001mm e 0.05 mm, preferibilmente tra 0.005 e 0.015 mm e da granulato di materiale lapideo oppure di materiale litoide preferibilmente selezionato tra 0.05 mm e 10 mm, ancora più preferibilmente tra 0.1 e 4.8 mm. According to a further aspect of the invention, the particles of said stone material or lithoid material have an average grain size between 0.001 mm and 10 mm, preferably between 0.010 mm and 5 mm; more particularly, said particles of stone material or lithoid material are made of quartz filler (also called ventilated powder) having an average grain size between 0.001mm and 0.05 mm, preferably between 0.005 and 0.015 mm and of granulate of stone material or lithoid material preferably selected between 0.05 mm and 10 mm, even more preferably between 0.1 and 4.8 mm.
Per un migliore risultato finale, detta resina à ̈ costituita da 30 a 70 parti in peso di detto trigliceride di acidi grassi polinsaturi epossidati, preferibilmente da 40 a 60; da 40 a 80 parti in peso di detta anidride di origine terpenica, preferibilmente da 50 a 70; da 1.5 a 2.5 parti in peso di detto iniziatore di catalisi, preferibilmente da 1.75 a 2.25; da 0.5 a 1.5 parti in peso di detto polialcol, preferibilmente da 0.75 a 1.25; da 0.5 a 1.5 parti in peso di detto silano, preferibilmente da 0.75 a 1.25. For a better final result, said resin consists of 30 to 70 parts by weight of said triglyceride of epoxidized polyunsaturated fatty acids, preferably from 40 to 60; from 40 to 80 parts by weight of said anhydride of terpenic origin, preferably from 50 to 70; from 1.5 to 2.5 parts by weight of said catalysis initiator, preferably from 1.75 to 2.25; from 0.5 to 1.5 parts by weight of said polyalcohol, preferably from 0.75 to 1.25; from 0.5 to 1.5 parts by weight of said silane, preferably from 0.75 to 1.25.
Vengono inoltre utilizzate da 3 a 20 parti in peso di dette particelle di materiale lapideo oppure di materiale litoide, preferibilmente da 5 a 15, per una parte in peso di detta resina a base di trigliceride di acidi grassi polinsaturi epossidati ed anidride da fonti terpeniche. Furthermore, from 3 to 20 parts by weight of said stone material or lithoid material particles are used, preferably from 5 to 15, for one part by weight of said resin based on triglyceride of epoxidized polyunsaturated fatty acids and anhydride from terpene sources.
Secondo un ulteriore aspetto, la reazione di indurimento della resina avviene a temperatura compresa tra 80 e 180 °C, preferibilmente tra 110 e 150 °C. According to a further aspect, the hardening reaction of the resin takes place at a temperature comprised between 80 and 180 ° C, preferably between 110 and 150 ° C.
L’esempio che segue illustra a titolo non limitativo il procedimento della presente invenzione. The following example illustrates the process of the present invention by way of a non-limiting example.
Esempio Example
184 g di olio di lino epossidato sono stati miscelati con 220 g di anidride dell’acido 3,4-dimetil-6-(2-metil-1-propenil)-4-cicloesen-1,2-dicarbossilico. Sono stati aggiunti 3.7 g di glicerina, 7.6 g di 1-metilimidazolo, 4.2 g di (3-glicidossipropil) trimetossi silano. La miscela à ̈ stata mescolata a temperatura ambiente per almeno 15 minuti. La resina così ottenuta à ̈ stata versata in una miscela di 3.255 g di granulato di quarzo avente una dimensione compresa tra 0.1 e 1.2 mm e 1.330 g di polveri ventilate aventi granulometria media compresa fra 0.005 e 0.025 mm. L’impasto viene mescolato, versato in uno stampo ed infine vibrocompattato, indurito e lucidato secondo il metodo standard Bretonstoneâ„¢. Il manufatto così ottenuto à ̈ stato sottoposto a prove di flessione, di assorbimento d’acqua e di resistenza all’abrasione profonda. Si à ̈ così riscontrato che: presenta una resistenza alla flessione pari a circa 60 MPa; se sottoposto ad assorbimento d’acqua per almeno 24 ore esibisce un incremento di peso pari a 0,03 %; alla prova di abrasione profonda genera un’impronta la cui corda à ̈ lunga 30 mm. 184 g of epoxidized linseed oil were mixed with 220 g of 3,4-dimethyl-6- (2-methyl-1-propenyl) -4-cyclohexene-1,2-dicarboxylic acid anhydride. 3.7 g of glycerin, 7.6 g of 1-methylimidazole, 4.2 g of (3-glycidoxypropyl) trimethoxy silane were added. The mixture was mixed at room temperature for at least 15 minutes. The resin thus obtained was poured into a mixture of 3,255 g of quartz granulate having a size between 0.1 and 1.2 mm and 1,330 g of ventilated powders having an average particle size between 0.005 and 0.025 mm. The mixture is mixed, poured into a mold and finally vibro-compacted, hardened and polished according to the standard Bretonstoneâ „¢ method. The resulting artifact was subjected to bending, water absorption and resistance to deep abrasion tests. It was thus found that: it has a flexural strength of approximately 60 MPa; if subjected to water absorption for at least 24 hours it exhibits a weight increase of 0.03%; to the deep abrasion test it generates an imprint whose rope is 30 mm long.
Claims (23)
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IT000125A ITTV20110125A1 (en) | 2011-09-20 | 2011-09-20 | PROCESS FOR THE PREPARATION OF MANUFACTURED ARTICLES IN GRANULATE CONGLOMERATE OF STONE MATERIAL AND RESIN WITH THERAPEUTIC ORIGIN |
PCT/IB2012/054789 WO2013042019A1 (en) | 2011-09-20 | 2012-09-14 | Process for preparing manufactured products in conglomerate of granulate of stone material and resin with anhydrides from renewable sources |
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DE202013104133U1 (en) * | 2013-09-11 | 2013-10-15 | Michael Sorge | Polymer material based on renewable raw materials |
US10913829B2 (en) | 2017-06-22 | 2021-02-09 | ACS Technical Products, Inc. | Epoxidized oil binder compositions and process for preparation of thermoset hardened products |
WO2018237177A1 (en) | 2017-06-22 | 2018-12-27 | ACS Technical Products, Inc. | Epoxidized oil and resin compositions |
IT201700102110A1 (en) * | 2017-09-12 | 2019-03-12 | Rosa Riccardo Salvatore La | Compound, stone-reinforced with low weight, obtained from waste sludge and dust from stone processing, recovery process from processing and method for the use of said waste materials inside the production plant or at external facilities |
IT201900010329A1 (en) * | 2019-06-27 | 2020-12-27 | Luca Toncelli | Artifact in conglomerate material, composite assembly comprising the artifact and method of production of the artifact in conglomerate material |
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